CN110003004A - A kind of method of step insertion synthesizing propanediol ether acetate - Google Patents
A kind of method of step insertion synthesizing propanediol ether acetate Download PDFInfo
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- CN110003004A CN110003004A CN201910291556.3A CN201910291556A CN110003004A CN 110003004 A CN110003004 A CN 110003004A CN 201910291556 A CN201910291556 A CN 201910291556A CN 110003004 A CN110003004 A CN 110003004A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The present invention relates to a kind of methods of step insertion synthesizing propanediol ether acetate, are using ethyl acetate and propylene oxide as raw material, magnesium-aluminum-zirconium complex solid alkali is catalyst, and closed stirring, uses N in a kettle2Air in kettle is displaced, set temperature is heated to, reacts synthesizing propanediol ether acetate；It is ethyl acetate that the reaction process condition, which is material molar ratio: propylene oxide=3~7:1, and reaction temperature is 110~150 DEG C, and catalyst quality percentage is the 1~3% of gross mass；The magnesium-aluminum-zirconium complex solid base catalyst is prepared using coprecipitation, and is made by high-temperature roasting.The invention has the advantages that the step embedding inlay technique synthesizing propanediol ether acetate being catalyzed using magnesium-aluminum-zirconium complex solid base catalyst, waste water is not generated compared to traditional esterifying reaction method, environmental pollution is small, reaction condition is mild, equipment is corroded small, low energy consumption, and post-processing is simple, fully demonstrates environmental protection and develops the green chemical industry theory of harmonious coexistence.
Description
Technical field
The invention belongs to technology of fine chemicals, and in particular to the synthesis of propylene-glycol ethyl ether acetic acid esters, specifically second
Acetoacetic ester and propylene oxide are raw material, and under the catalysis of magnesium-aluminum-zirconium complex solid base catalyst, propylene oxide open loop is embedded in acetic acid
Ethyl ester synthesizing propanediol ether acetate.
Background technique
Propylene glycol ether-ether is the favorable substitutes of glycol ether ester, and as " alembroth " of new generation, toxicity is smaller, together
When have solubility property similar with glycol ether ester.Propylene-glycol ethyl ether acetic acid esters be propylene glycol ether-ether series staple product it
One, it is widely used in the industries such as coating, pigment, ink, efficient cleaner, printing, leather and electronic chemical product.
Direct esterification is the method for the synthesizing propanediol ether acetate industrially generallyd use at present, can be generated a large amount of
Waste water, and there is the problems such as perishable to equipment, post-processing complexity, pollution environment.It needs us and develops a kind of efficient, environment
Friendly technique, creates conditions for industrialization.And a step embedding inlay technique synthesizing propanediol ether acetate does not generate industrial wastewater, it is former
Material is easy to get, simple process, and reaction is mild, small to equipment corrosion, and low energy consumption, and post-processing is simple, and environmental pollution is small.Cause chemistry
The interest of worker and greatly concern.
Summary of the invention
The purpose of the present invention is to provide a kind of method of step insertion synthesizing propanediol ether acetate, this method is avoided
Equipment caused by conventional homogeneous acidic catalyst is corroded, and catalyst is difficult the problems such as separating with product, simple process, energy consumption
It is low, and catalyst is easily separated, reusable, energy conservation and environmental protection.
The object of the present invention is achieved like this: ethyl acetate, catalyst being added in reaction kettle, sealing stirring is used
N2Air in kettle is displaced, set temperature is heated to, propylene oxide is slowly introducing and to control reactor temperature substantially permanent
It is fixed, control reacting kettle inner pressure in 0.20~0.50MPa, after propylene oxide is passed through setting quality, continue under established temperature into
Row reaction, until pressure is constant in kettle, and remains unchanged in 30min, cools down after reaction and discharge, obtain propylene-glycol ethyl ether
Acetic acid esters product.
The catalyst is magnesium-aluminum-zirconium complex solid base catalyst.
Magnesium-aluminum-zirconium complex solid base catalyst provided by the invention is prepared in accordance with the following methods: by MgCl2·6H2O、
Al(NO3)3·9H2O、ZrOCl2·8H2O is configured to the salting liquid that concentration is 20% with deionized water, by sodium hydroxide and carbonic acid
Sodium is configured to the precipitating reagent that concentration is 15% with deionized water, and precipitating reagent is first added into flask, adds salting liquid, acutely stirs
It mixes down and is warming up to set temperature, reaction crystallization filters out sediment after a certain period of time, will be adhered on sediment with deionized water
Soluble-salt washing removes, dry to constant weight, grinding, is placed in Muffle furnace roasting at a certain temperature and obtains magnesium-aluminum-zirconium composite solid
Body base catalyst.
It is limited as to another step of the invention, raw material molar ratio is ethyl acetate: ring in the method for the invention
Ethylene Oxide=3~7:1, reaction temperature are 110~150 DEG C, and reaction pressure is 0.20~0.50MPa, and catalyst amount is raw material
The 1~3% of gross mass.
It is limited as to another step of the invention, feed molar more suitable proportion is acetic acid in the method for the invention
Ethyl ester: propylene oxide=6:1, reaction temperature are 130 DEG C, and catalyst amount is the 2% of total mass of raw material, used in catalyst preparation
Magnesium-aluminum-zirconium cation mole ratio is n (Mg in salting liquid2+): n (Al3+): n (Zr4+)=1:0.65:0.04, n in precipitating reagent
(NaOH): n (Na2CO3)=1:1, crystallization temperature are 70 DEG C, crystallization time 7h, and catalyst maturing temperature is 400 DEG C, when roasting
Between be 5h.
The composite oxide catalysts can be separated through filtering with product, can be recycled, environmental protection and economy.
The invention has the advantages that not generating waste water in a step embedding inlay technique reaction process, raw material is cheap and easy to get, process flow letter
Single, complex solid base catalyst used is small to equipment corrosion, and easily separated with product, post-reaction treatment is simple, and reaction condition is mild,
Low energy consumption, and no pollution to the environment, product yield is higher, and selectivity is good.
Specific embodiment
Invention is described further by following instance, but is not intended to limit the present invention.
In embodiment, propylene-glycol ethyl ether acetic acid esters is containing there are two types of isomers, respectively 1- ethyoxyl -2- propyl acetate
(1-PEA) and 2- ethyoxyl -1- propyl acetate (2-PEA), industry is interior to be generally called propylene-glycol ethyl ether acetic acid esters.Since product PEA can
Further to react with propylene oxide, therefore contain a small amount of dipropylene glycol ethyl ether acetic acid esters (DPEA) in product.With propylene oxide
Conversion ratio and the yield of product 1-PEA, 2-PEA and DPEA be that index determines the activity of catalyst.Each substance in product
Content is to carry out quantitative analysis with gas chromatography.Using GC9790 type gas chromatograph, split sampling, it is furnished with temperature programming
Component, flame ionization ditector.Capillary chromatograph stationary phase is PEG20000, and specification is 30m × 0.32mm × 0.45 μm.
In embodiment, the conversion ratio of propylene oxide (PO) and the yield of propylene-glycol ethyl ether acetic acid esters are according to the following formula
It obtains:
Embodiment 1
211.46g ethyl acetate and 2.46g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 34.96g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa.Wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, and catalyst amount is the total matter of reactant
The 1% of amount.Epoxypropane conversion rate is that 24.68%, PEA yield is that 12.27% (wherein 1-PEA yield is 8.79%, 2-PEA
Yield is that 3.48%), DPEA yield is 12.41%.
Embodiment 2
211.46g ethyl acetate and 3.70g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 34.96g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, catalyst amount is the total matter of reactant
The 1.5% of amount.Epoxypropane conversion rate is that 45.16%, PEA yield is that 34.45% (wherein 1-PEA yield is 24.20%, 2-
PEA yield is that 10.25%), DPEA yield is 10.71%.
Embodiment 3
211.46g ethyl acetate and 4.93g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 34.96g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is 63.55%；PEA yield is that 46.76% (wherein 1-PEA yield is 34.24%；2-PEA
12.52%) yield is；DPEA yield is 16.79%.
Embodiment 4
211.46g ethyl acetate and 6.16g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 34.96g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, catalyst amount is the total matter of reactant
The 2.5% of amount.Epoxypropane conversion rate is 55.37%；PEA yield is that 43.12% (wherein 1-PEA yield is 31.01%；2-
12.11%) PEA yield is；DPEA yield is 12.25%.
Embodiment 5
211.46g ethyl acetate and 7.39g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 34.96g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, catalyst amount is the total matter of reactant
The 3% of amount.Epoxypropane conversion rate is that 54.06%, PEA yield is that 42.47% (wherein 1-PEA yield is 30.52%, 2-PEA
Yield is that 11.95%), DPEA yield is 11.59%.
Embodiment 6
211.46g ethyl acetate and 5.16g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 46.46g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=3:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 58.19%, PEA yield is that 45.64% (1-PEA yield is 32.52%, 2-PEA yield
For 13.12%), DPEA yield is 12.55%.
Embodiment 7
220.28g ethyl acetate and 4.99g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 29.04g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=5:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 64.53%, PEA yield is 50.27%, and (wherein 1-PEA yield is 35.36%；2-
PEA yield is that 14.91%), DPEA yield is 14.26%.
Embodiment 8
237.9g ethyl acetate and 5.28g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 26.14g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=6:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 66.16%, PEA yield is that 53.59% (wherein 1-PEA yield is 38.34%；2-PEA
Yield is that 15.25%), DPEA yield is 12.58%.
Embodiment 9
246.71g ethyl acetate and 5.40g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 23.23g into reaction kettle after temperature reaches 130 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=7:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 56.53%, PEA yield is that 46.94% (wherein 1-PEA yield is 33.59%；2-PEA
Yield is that 13.35%), DPEA yield is 9.58%.
Embodiment 10
237.9g ethyl acetate and 5.28g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stirring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 26.14g into reaction kettle after temperature reaches 110 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=6:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 12.63%, PEA yield is that 9.66% (wherein 1-PEA yield is 7.10%；2-PEA is produced
Rate is that 2.56%), DPEA yield is 2.96%.
Embodiment 11
237.9g ethyl acetate and 5.28g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stiring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 26.14g into reaction kettle after temperature reaches 120 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=6:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 22.35%, PEA yield is that 17.85% (1-PEA yield is 13.39%；2-PEA yield
For 4.46%), DPEA yield is 4.49%.
Embodiment 12
237.9g ethyl acetate and 5.28g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stiring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 26.14g into reaction kettle after temperature reaches 140 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=6:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is 66.24%；PEA yield is that 53.1% (wherein 1-PEA yield is 37.57%, 2-PEA
15.53%) yield is；DPEA yield is 13.14%.
Embodiment 13
237.9g ethyl acetate and 5.28g magnesium-aluminum-zirconium complex solid base catalyst are added to the reaction kettle of 2L under stiring
In, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature liter
Temperature is passed through propylene oxide 26.14g into reaction kettle after temperature reaches 150 DEG C and stablizes, and reacting kettle inner pressure is 0.20~
0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=6:1, catalyst amount is the total matter of reactant
The 2% of amount.Epoxypropane conversion rate is that 66%, PEA yield is that 53.5% (wherein 1-PEA yield is 37.81%, 2-PEA yield
For 15.69%), DPEA yield is 12.49%.
Embodiment 14
By 211.46g ethyl acetate and 4.93g magnesium-aluminum-zirconium complex solid base catalyst, (catalyst is from anti-under stiring
It answers in liquid and separates, the 4th recycling) it is added in the reaction kettle of 2L, feed inlet is closed, checks reaction kettle air-tightness, confirmation
Air in kettle, set temperature heating, after temperature reaches 130 DEG C and stablizes, to reaction kettle are displaced with N2 after device is air tight
In be passed through propylene oxide 34.96g, reacting kettle inner pressure is 0.20~0.50MPa, wherein the reaction raw materials molar ratio is acetic acid
Ethyl ester: propylene oxide=4:1, catalyst amount are the 2% of reactant gross mass.Epoxypropane conversion rate is 57.41%, PEA
Yield is 39.79%, and (it is that 14.82%), DPEA yield is 17.62% that wherein 1-PEA yield, which is 24.97%, 2-PEA yield,.
Comparative example 1
211.46g ethyl acetate and 4.93g magnalium solid base catalyst are added to the reaction that volume is 2L under stiring
In kettle, feed inlet is closed, reaction kettle air-tightness is checked, uses N after confirmation device is air tight2Displace air in kettle, set temperature
Heating, after temperature reaches 130 DEG C and stablizes, propylene oxide 34.96g, reacting kettle inner pressure 0.20 are passed through into reaction kettle
~0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, magnalium solid base catalyst aluminium sun
Ion molar ratio is n (Mg2+): n (Al3+) :=1:0.65 is free of zirconium, and dosage is the 2% of reactant gross mass.Propylene oxide turns
Rate be 36.52%, PEA yield be 24.45% (wherein 1-PEA yield be 13.56%, 2-PEA yield be 10.89%),
DPEA yield is 12.07%.
Comparative example 2
It is 2L that 211.46g ethyl acetate and 4.93g magnesium-aluminum-calcium complex solid base catalyst, which are added to volume, under stiring
Reaction kettle in, close feed inlet, check reaction kettle air-tightness, confirmation device it is air tight after use N2Air in kettle is displaced, if
Determine temperature heating, after temperature reaches 130 DEG C and stablizes, propylene oxide 34.96g, reacting kettle inner pressure are passed through into reaction kettle
For 0.20~0.50MPa, wherein the reaction raw materials molar ratio is ethyl acetate: propylene oxide=4:1, catalyst n (Mg2+): n
(Al3+): n (Ca2+)=1:0.65:0.04, dosage are the 2% of reactant gross mass.Epoxypropane conversion rate is 44.71%,
PEA yield is 24.96%, and (it is that 9.11%), DPEA yield is 19.75% that wherein 1-PEA yield, which is 15.85%, 2-PEA yield,.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (5)
1. a kind of method of step insertion synthesizing propanediol ether acetate, it is characterised in that: ethyl acetate, magnesium-aluminum-zirconium is compound
Solid base catalyst is added in reaction kettle, and N is used in sealing stirring2Air in kettle is displaced, set temperature is heated to, is delayed
Slowly it is passed through propylene oxide, and controls reactor temperature substantially constant, control reacting kettle inner pressure in 0.20~0.50MPa, instead
Cool down after answering and discharge, obtains propylene-glycol ethyl ether acetic acid esters product.
2. a kind of method of step insertion synthesizing propanediol ether acetate according to claim 1, it is characterised in that:
Material molar ratio is ethyl acetate: propylene oxide=3~7:1, reaction temperature be 110~150 DEG C, reaction pressure be 0.20~
0.50MPa, magnesium-aluminum-zirconium complex solid base catalyst are the 1~3% of total mass of raw material.
3. the method that one step of one kind according to claims 1 or 2 is embedded in synthesizing propanediol ether acetate, feature exist
In: material molar ratio is ethyl acetate: propylene oxide=6:1；Reaction temperature is 130 DEG C；Catalyst amount is the total matter of reactant
The 2% of amount.
4. a kind of method of step insertion synthesizing propanediol ether acetate according to claim 1 or 2, feature exist
In: the magnesium-aluminum-zirconium complex solid base catalyst the preparation method is as follows: by MgCl2·6H2O、Al(NO3)3·9H2O、
ZrOCl2·8H2O is configured to the salting liquid that concentration is 20% with deionized water, and sodium hydroxide and sodium carbonate deionized water are matched
It is set to the precipitating reagent that concentration is 15%, precipitating reagent is first added into flask, adds salting liquid, is vigorously stirred down and is warming up to setting
Temperature, reaction crystallization filter out sediment after a certain period of time, wash the soluble-salt adhered on sediment with deionized water and remove
It goes, it is dry to constant weight, grinding, it is placed in Muffle furnace roasting at a certain temperature and obtains magnesium-aluminum-zirconium complex solid base catalyst.
5. a kind of method of step insertion synthesizing propanediol ether acetate according to claim 4, it is characterised in that: magnesium
Aluminium zirconium cation mole ratio is n (Mg2+): n (Al3+): n (Zr4+)=1:0.65:0.04, molar ratio n (NaOH): n in precipitating reagent
(Na2CO3)=1:1, crystallization temperature are 70 DEG C, crystallization time 7h, and catalyst maturing temperature is 400 DEG C, calcining time 5h.
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| CN116440892A (en) * | 2023-04-28 | 2023-07-18 | 盐城工学院 | Catalyst for preparing propylene glycol monoethyl ether and preparation method thereof |
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